Use of isomeric mixtures of farnesene for augmenting or enhancing the aroma of detergent compositions

ABSTRACT

Described are isomeric mixtures of farnesene prepared by dehydrating nerolidol using potassium bisulfate or paratoluene sulfonic acid and then distilling the resultant product at particular temperature ranges and particular pressure ranges in order to prepare a composition of matter useful for augmenting or enhancing waxy, white-flowery (magnolia-like, tuberose, gardenia-like) aromas with citrusy (lemon/lime), pettitgrain-like undertones and green top notes in perfume compositions, colognes and perfumed articles (e.g., solid or liquid anionic, cationic, nonionic or zwitterionic detergents, fabric softener compositions, dryer-added fabric softener articles, cosmetic powders and the like).

This is a divisional of application Ser. No. 292,392, filed Aug. 13,1981 now U.S. Pat. No. 4,376,068.

BACKGROUND OF THE INVENTION

The present invention relates to farnesene isomer mixtures containing,but not limited to, compounds defined according to the structures:##STR1## and uses of such mixtures in augmenting or enhancing the aromaof perfume compositions, perfumed articles and colognes. Thecompositions of our invention are prepared by dehydrating usingpotassium bisulfate or paratoluene sulfonic acid dehydrating agents,nerolidol compositions of matter containing the nerolidol isomers:##STR2##

There has been considerable work performed related to substance whichcan be used to impart (modify, augment or enhance) fragrances to (or in)various consumable materials. The substances are used to diminish theuse of natural materials, some of which may be in short supply and toprovide more uniform properties in the finished product.

Waxy, white-flowery (magnolia-like, tuberose and gardenia-like) aromawhich are very close to the corresponding natural magnolia-like,tuberose and gardenia-like aromas, with citrusy (lemon/lime),pettitgrain-like undertones and green top notes are particularlydesirable in several types of perfume compositions, perfumed articlesand colognes.

Such aromas with the floral wet petal "morning dew" aromas are even moreinteresting in the field of perfumery.

Arctander "Perfume and Flavor Chemicals (Aroma Chemicals)" at monograph1378 discloses "Farnesal", 2,6,10-trimethyl-2,6,10-dodecatrien-12-al tohave a very mild, sweet oily, slightly woody, tenacious odor. On theother hand, Arctander also describes, at Monograph 1379, Farnesene,2,6,10-trimethyl-2,6,9,11-dodecatetraene defined according to thestructure: ##STR3## to have a very mild, sweet and warm, rathernondescript odor of good tenacity. Arctander further states that apartfrom some possible use in the reconstruction of certain essential oils,there is to the author's knowledge, very little, if any, use for thissesquiterpene in perfumery as such. Arctander further states thatFarnesene having the structure: ##STR4## is produced by dehydration ofFarnesol by heat with a potassium dehydrating agent or from Nerolidol byheat with acetic anhydride.

Brieger, et al, J. Org. Chem. Volume 34, Number 12, December 1969, intheir paper "The Synthesis of trans,trans-α-Farnesene" disclosesdehydration of nerolidol using bisulfate at 170° C. to yield a number ofFarnesene isomers according to the reaction: ##STR5## Brieger, et alalso discloses the dehydration of Farnesol using potassium bisulfate at170° C. as follows: ##STR6## Brieger also teaches the dehydration ofFarnesol using potassium hydroxide at 210° C. to yield certain isomersaccording to the following reaction: ##STR7##

Anet, Aust. J. Chem., 1970, 23, 2101-8, in a paper entitled "Synthesisof (E,Z)-α-, (Z,Z)-α-, and (Z)-β-Farnesene" discloses the dehydration of(E)-nerolidol having the structure: ##STR8## in the presence of suchdehydrating agents as phosphoryl chloride in pyridene to yield thecompounds having the structures: ##STR9## according to the reaction:##STR10##

In a paper by Hattori, et al entitled "Chemical Composition of theAbsolute from Gardenia Flower" and in another paper by Tsuneya, et alentitled "GC-MS Analysis of Gardenia Flower Volatiles", it is disclosedthat α-farnesene is existent in gardenia flower absolute. The Hattori,et al and Tsuneya, et al papers are published in the "VII InternationalCongress of Essential Oils; Japan Flavor and Fragrance Manufacturers'Association, Tokyo (1979) at pages 451 and 454, respectively (papers 128and 129, respectively).

Nothing in the prior art cited above indicates the subject matter of ourinvention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. A is the GLC profile for the nerolidol used as a reactant inExample I.

FIG. B is the GLC profile for the nerolidol used as a reactant inExample III.

FIG. 1 is the GLC profile subsequent to basic wash but prior todistillation for the reaction product of Example I.

FIG. 2 is the GLC profile for bulked frations 4-18 of the distillationproduct of the reaction product of Example I.

FIG. 2(A) is the infra-red spectrum for bulked fractions 4-18 of thedistillation product of the reaction product of Example I.

FIG. 3 is the infra-red spectrum for peak 11 of the GLC profile of FIG.2.

FIG. 4 is the infra-red spectrum for peak 12 of the GLC profile of FIG.2.

FIG. 5 is the infra-red spectrum of peak 13 of the GLC profile of FIG.2.

FIG. 6 is the infra-red spectrum for peak 14 of the GLC profile of FIG.2.

FIG. 7 is the NMR spectrum for peak 11 of the GLC profile of FIG. 2.

FIG. 8 is the NMR spectrum for peak 12 of the GLC profile of FIG. 2.

FIG. 9 is the NMR spectrum for peak 13 of the GLC profile of FIG. 2.

FIG. 10 is the NMR spectrum for peak 14 of the GLC profile of FIG. 2.

FIG. 11 is the mass spectrum for peak 11 of the GLC profile of FIG. 2.

FIG. 12 is the mass spectrum for peak 12 of the GLC profile of FIG. 2.

FIG. 13 is the mass spectrum for peak 13 of the GLC profile of FIG. 2.

FIG. 14 is the mass spectrum for peak 14 of the GLC profile of FIG. 2.

FIG. 15 is the GLC profile for the magnolia headspace of Example II.

FIG. 16(A) is the GLC profile for the crude reaction product of ExampleIII.

FIG. 16(B) is the GLC profile for fraction 1 of the distillation productof the reaction product of Example III.

FIG. 16(C) is the GLC profile for fraction 2 of the distillation productof the reaction product of Example III.

FIG. 16(D) is the GLC profile for fraction 3 of the distillation productof the reaction product of Example III.

FIG. 16(E) is the GLC profile for fraction 4 of the distillation productof the reaction product of Example III.

FIG. 16(F) is the GLC profile for fraction 5 of the distillation productof the reaction product of Example III.

FIG. 16(G) is the GLC profile for fraction 6 of the distillation productof the reaction product of Example III.

FIG. 16(H) is the GLC profile for fraction 7 of the distillation productof the reaction product of Example III.

FIG. 16(J) is the GLC profile for fraction 8 of the distillation productof the reaction product of Example III.

FIG. 16(K) is the GLC profile for fraction 9 of the distillation productof the reaction product of Example III.

FIG. 16(L) is the GLC profile for bulked fractions 4-7 of thedistillation product of the reaction product of Example III.

FIG. 17 is the infra-red spectrum for bulked fractions 4-17 of thedistillation product of the reaction product of Example III.

FIG. 18 is the GLC profile for the crude reaction product of Example IV.

FIG. 19 is the GLC profile for bulked fractions 4-8 of the distillationproduct of the reaction product of Exaple IV.

DETAILED DESCRIPTION OF THE DRAWINGS A. DETAILED DESCRIPTION OF FIGURE A

Figure A is the GLC profile for the nerolidol reactant used for ExampleI. Reference numeral 25A and reference numeral 25B indicate thenerolidol reactant peaks for the compounds having the structures:##STR11## The GLC conditions are: 5% Carbowax 10'×1/8" column programmedat 100°-230° C. at 4° C. per minute.

Figure B is the GLC profile for the nerolidol reactant used in ExampleIII. Reference numeral 35A and 35B indicate the peaks for the nerolidolreactant on this GLC profile. The nerolidol reactants have thestructures: ##STR12## The GLC conditions are: 10'×1/8" 5% Carbowaxcolumn programmed at 100°-230° C. at 4° C. per minute.

FIG. 1 is the GLC profile for the reaction product of Example Isubsequent to the base wash but prior to distillation. The GLCconditions are: 10'×1/8" 5% Carbowax column programmed at 100°-220° C.at 4° C. per minute. The peak indicated by reference numeral 1 indicatesthe compound having the structure: ##STR13## The peak indicated byreference numeral 2 is for the compound having the structure: ##STR14##The peak indicated by reference numeral 3 is for the compound having thestructure: ##STR15## The peak indicated by reference numeral 4 is forthe compounds having the structures: ##STR16## wherein the structure:##STR17## represents a mixture of compounds wherein in each of themolecules of the mixture, one of the dashed lines represents a pi doublebond and each of the other of the dashed lines are indicative of singlebonds. The peaks indicated by reference numerals 5A and 5B are isomersof nerolidol, the starting material, said nerolidol having thestructures: ##STR18##

FIG. 2 is the GLC profile for bulked fractions 4-18 of the distillationproduct of the reaction product of Example I containing isomers offarnesene and isomers of nerolidol. Conditions: 10'×1/8" 5% Carbowaxcolumn programmed at 100°-220° C. at 4° C. per minute. The peakindicated by reference numeral 11 is for the compound having thestructure: ##STR19## The peak indicated by reference numeral 12 is forthe compound having the structure: ##STR20## The peak indicated byreference numeral 13 is for the compound having the structure: ##STR21##The peak indicated by reference numeral 14 is the for compounds definedaccording to the structures: ##STR22## wherein the structure: ##STR23##is indicative of a mixture wherein in each of the molecules of themixture, one of the dashed lines represents a pi double bond and each ofthe other of the dashed lines is indicative of a single bond. The peaksindicated by reference numeral 15A and 15B are for isomers of nerolidolhaving the structures: ##STR24##

FIG. 15 is the GLC profile for the magnolia headspace produced accordingto Example II. The peak indicated by reference 16 is for α-farnesenewhich contains compounds having the structures: ##STR25## among othercompounds. The conditions for this GLC profile are: SF 96 column,isothermal, 190° C.

FIG. 18 is the GLC profile for the crude reaction product of Example IV.The conditions for this GLC profile are: 10'×1/8" 5% Carbowax columnprogrammed at 220° C. isothermal. The peaks indicated by referencenumerals 17A and 17B are for various farnesene isomers containing,interalia, the compound having the structure: ##STR26## The peaksindicated by reference numerals 18A, 18B and 18C are for farnesylacetate isomers having the structures: ##STR27##

FIG. 19 is the GLC profile for bulked fractions 4-8 of the distillationproduct of the reaction product of Example IV. The conditions for thisGLC profile are: 10'×1/8" 5% Carbowax column programmed at 200° C.isothermal. The peaks indicated by reference numeral 19A, 19B, 19C and19D are for farnesene isomers containing the compound having thestructure: ##STR28## as well as other compounds.

THE INVENTION

It has now been discovered that novel solid and liquid perfumecompositions, colognes and perfumed articles having very natural, waxy,flowery, wet petal (reminiscent of magnolia, tuberose and gardenia)aromas with citrusy (lemon/lime), petitgrain-like undertones and greentop notes may be provided by an isomeric mixture of farnesenederivatives (containing a number of other compounds) defined accordingthe process for producing same by the dehydration of various isomericmixtures of E(trans) and Z(cis) nerolidol having the structures:##STR29## using a potassium acid sulfate or paratoluene sulfonic aciddehydration catalyst over a particular temperature and pressure rangefor a given reaction time range.

The reaction to produce the products of our invention may be set forthas follows: ##STR30## wherein the catalyst used may be potassium acidsulfate (KHSO₄) or paratoluene sulfonic acid.

The ratio of E(trans) or Z(cis) nerolidol isomers having the structures:##STR31## used in the reaction mass may vary from 25:100 E isomer:Zisomer up to 100:25 E isomer:Z isomer. Although the isomer mixture issubstantially the same whether using the paratoluene sulfonic acidcatalyst or the potassium acid sulfate catalyst, the specific reactionconditions using the two catalysts are different.

Thus, when using a potassium acid sulfate catalyst, the temperaturerange is preferably between 180° and 200° C. and it is necessary toutilize a solvent for the reaction mass which will:

(a) be inert to the reaction;

(b) have a boiling point at the reaction pressure which will beconveniently greater than the reaction temperature so that the solventwill not volatilize from the reaction mass.

Thus, when using a potassium acid sulfate catalyst at a temperature inthe range of 180°-200° C., it is most preferable to use a heavyhydrocarbon mineral oil, for example, Primol® (manufactured by the ExxonCorporation of Linden, New Jersey). Other inert solvents such as tolueneand xylene may be used but, when using toluene, the pressure over thereaction mass must be such that the reaction mass will reflux in therange of 180°-200° C. Thus, when using a toluene or xylene solvent, apositive nitrogen pressure over the reaction mass is necessary in orderto maintain the reaction temperature at 180°-200° C. Thus, when using apotassium acid sulfate catalyst, not only is the temperature rangeimportant, e.g., 180°-200° C., but the pressure range is equally asimportant; from 1 up to 200 atmospheres pressure. Using pressuresgreater than 1 atmosphere necessitates the use of high pressureequipment and appropriate safety proportions.

Whether using a potassium acid sulfate catalyst or a paratoluenesulfonic acid catalyst, it is necessary to remove the water of reactionas it is formed. Thus, during refluxing, a phase separation column isnecessarily utilized whereby the water of reaction is removed during thecourse of the reaction. For example, a Bidwell water trap is the type oftrap used in the laboratory when removing the water of reaction.

Accordingly, the time of reaction is necessarily dictated by the rate atwhich the nerolidol reaction mixture is added to the catalyst/solventmixture. It is preferable to add the nerolidol to the catalyst/solventmixture over a period of between 5 and 20 hours.

When using a paratoluene sulfonic acid catalyst, the reactiontemperature range may vary from 115° C. (reflux at atmospheric pressure)using a toluene solvent up to 200° C. (reflux, preferably using atoluene or xylene solvent at higher pressures). Thus, the reactiontemperature range is considerably greater in scope when using theparatoluene sulfonic acid catalyst than when using the potassium acidsulfate catalyst. Furthermore, the solvent used may be toluene, xyleneor a heavy hydrocarbon mineral oil so long as the solvent is inert tothe reaction product and is inert to the reactant.

Significantly, the use of the paratoluene sulfonic acid catalyst carrieswith it a certain definitive advantage over the use of all otherdehydration catalysts including the potassium acid sulfate; that is, theversatility of equipment that can be used with paratoluene sulfonic acidas opposed to, for example, potassium acid sulfate. The paratoluenesulfonic acid catalyst's use gives rise to insignificant corrosionproblems when using steel reactors. Thus, when using a paratoluenesulfonic acid catalyst, the need for using glass-lined equipment orglass-lined reactors is obviated thereby significantly reducing thecapital equipment cost in the establishment of a plant for producing thefarnesene isomer mixtures of this invention. On the other hand, whenusing the potassium acid sulfate catalyst, although this catalyst givesrise to useful, unobvious and advantageous products, it is necessary todevise such equipment whereby little corrosion takes place during thecourse of the reaction. Such equipment will necessarily be eitherstainless steel or, more preferably, glass-lined equipment withappropriate accessories. When carrying out these reactions in acontinuous fashion, it is much more important to design equipmentwhereby the corrosion incidence will be minimal thereby requiringspecific low acid environment corrosion type alloys. The situationconcerning the use of continuous equipment gives rise to an even greaterneed to use either specific alloys when utilizing a potassium acidsulfate catalyst or utilizing a paratoluene sulfonic acid catalystwhereby standard continuous steel processing equipment may be utilized.

Significantly, whether using a potassium acid sulfate catalyst or aparatoluene sulfonic acid catalyst, no nerolidol acetates will be formedwhich is the case when using, for example, an acetic anhydridedehydration catalyst. The structures of the nerolidol esters are, whenusing an acetic anhydride catalyst: ##STR32##

Whether using a potassium acid sulfate catalyst or a paratoluenesulfonic acid catalyst, the ratio of catalyst to nerolidol may vary from1:1000 (wt/wt) up to 1:5 with a preferred ratio of 1:60 when using thepotassium acid sulfate catalyst and a preferred ratio of 1:500 whenusing the paratoluene sulfonic acid catalyst. The concentration ofcatalyst in the reaction mixture may vary from 1:2000 up to 1:100 with apreferred ratio of between 1:800 and 1:1,500 (wt/wt) being optimum.

The ratio of solvent:nerolidol isomer mixture varies depending upon theparticular solvent used and the desired catalyst concentration. Thus,when using a heavy hydrocarbon inert mineral oil and a potassium acidsulfate catalyst, the preferred ratio of solvent:nerolidol isomerreactants is between 1:1 and 1:4 with a most preferred ratio being 1:3.When using a toluent solvent or a xylene solvent, the preferredweight/weight ratio may vary from 1:2 up to 2:1 with a most preferredweight ratio of nerolidol isomer mixture:solvent being 1:1.

The product-by-process of our invention, the farnesene isomer mixture,and one or more auxiliary perfume ingredients including, for example,alcohols, aldehydes, ketones, nitriles, esters, cyclic esters(lactones), dialkyl ethers, alkyl alkenyl ethers, thioethers, thiols,carboxylic acids and hydrocarbons other than the farnesene isomericmixture of our invention and natural essential oils may be admixed sothat the combined odors of the individual components produce a pleasantand desired fragrance, particularly and preferably in wet petal, whiteflower fragrances, e.g., magnolia, gardenia and tuberose. Such perfumecompositions usually contain (a) the main note or the "bouquet" orfoundation stone of the composition; (b) modifiers which round off andaccompany the main notes; (c) fixatives which include odorous substanceswhich lend a particular note to the perfume throughout all states ofevaporation and substances which retard evaporation; and (d) top noteswhich are usually low-boiling, fresh-smelling materials.

In perfume compositions, it is the individual components whichcontribute to their particular olfactory characteristics, however, theoverall sensory effect of the perfume composition will be at least thesum total of the effects of each of the ingredients. Thus, the farneseneisomer mixture produced according to the process of our invention can beused to alter, modify or enhance the aroma characteristics of a perfumecomposition, for example, by utilizing or moderating the olfactoryreaction contributed by another ingredient in the composition.

The amount of farnesene isomer mixture of our invention which will beeffective in perfume compositions, as well as in perfumed articles andcolognes depends on many factors, including the other ingredients, theiramounts and the effects which are desired. It has been found thatperfume compositions containing as little as 0.01% of the farneseneisomer mixtures or evn less (e.g., 0.005%) can be used to impart a verynatural waxy, flowery, wet petal (reminiscent of magnolia, tuberose andgardenia) aroma which citrusy (lemon/lime), and petitgrain-likeundertones and green top notes to soaps, cosmetics and other products.The amount employed can range up to 70% of the fragrance components andwill depend on considerations of cost, nature of the end product, theeffect desired on the finished product and the particular fragrancesought.

The farnesene isomer mixture produced according to the process of ourinvention is useful (taken alone or together with other ingredients inperfume compositions) as (an) olfactory component(s) in detergents andsoaps, space odorants and deodorants, perfumes, colognes, toilet waters,bath preparations such as lacquers, brilliantines, pomades and shampoos;cosmetic preparations such as creams, deodorants, hand lotions and sunscreens; powders such as talcs, dusting powders, face powders, andperfumed article compositions of matter such as perfumed polypropylene,polyethylene and polyurethanes, partially long-lasting, partiallyshort-lasting mixtures of, for example, encapsulated perfumes suspendedin free perfume compositions and the like. When used as (an) olfactorycomponent(s), as little as 0.1% of the farnesene isomer mixture of ourinvention will suffice to impart an intense, waxy, flowery, wet petal(magnolia-like, tuberose and gardenia-like) aroma with citrusy(lemon/lime), petitgrain-like undertones and green top notes tomagnolia, gardenia, tuberose and other white flower formulations.Generally, no more than 3% of the farnesene isomer mixture of ourinvention based on the ultimate end product is required in the perfumecomposition.

In addition, the perfume composition of fragrance composition of ourinvention can contain a vehicle or carrier for the farnesene isomermixture. The vehicle can be a liquid such as non-toxic alcohol, (e.g.,ethyl alcohol), a non-toxic glycol (e.g., propylene glycol or1,2-butylene glycol or sorbitol) or the like. The carrier can also be anabsorbent solid such as a gum (e.g., gum arabic, xanthan gum or thelike) or components for encapsulating the composition (such as gelatinor ethyl cellulose) as by coacervation.

When used as a component of a perfumed article such as a perfumedplastic or a solid or liquid anionic, cationic, nonionic or zwitterionicdetergent, or a dryer-added fabric softener article or a fabric softenercomposition or a shampoo or a soap, the range of farnesene isomer usablevaries from 0.005% up to about 5% by weight of the perfumed article. Thelower range of this range, e.g., 0.005% up to 0.1% of the farneseneisomer mixture of our invention, is most preferred when using it in adryer-added fabric softener article or fabric softener composition inview of the need for a "non-perfumy" but pleasant head space aroma abovethe batch of clothes dried using the dryer-added fabric softener articleor fabric softener composition in a standard automatically operatedtumbler dryer.

It will thus be apparent that the farnesene isomer mixtures of ourinvention can be utilized to augment, alter, modify or enhance sensoryproperties, particularly organoleptic properties, of a wide variety ofconsumable materials.

Examples I and III, following, serve to illustrate the process forproducing the farnesene isomer mixture of our invention usable inpracticing Example V and examples following Example V. Example IIillustrates a process whereby α-farnesene isomers such as those havingthe structures: ##STR33## are isolated from the head space of magnolia.Example IV following, illustrates a process unworkable for the purposesof our invention using an acetic anhydride dehydrating agent producing,in addition to farnesene isomers, a mixture of isomers of farnesylesters.

It will be understood that these examples are illustrative, and theinvention is to be considered restricted thereto only as indicated inthe appended claims.

All parts and percentages given herein are by weight unless otherwisespecified.

EXAMPLE I PREPARATION OF MIXTURE OF FARNESENE ISOMERS USING A POTASSIUMACID SULFATE DEHYDRATION CATALYST ##STR34##

Into a five liter reaction flask equipped with stirrer, Rushover head,1' splash column with glass packing, thermometer, addition funnel, glass"Y" tube, heating mantle and vacuum set-up, is placed 1000 grams ofprimol® (a mineral oil manufactured by the Exxon Corporation of Linden,N.J.) and 50 grams of potassium acid sulfate (KHSO₄). The resultingmixture is heated to 185° C. and maintained at 185° C. for a period of15 minutes.

A mixture of nerolidol isomers defined according to the GLC profile setforth in FIG. "A" is placed in the addition funnel and, over a 10 hourperiod while maintaining the reaction mass temperature at 190° to 195°C. and maintaining a pressure above the reaction mass of 10-15 mm/Hg(vacuum), 3000 grams of the nerolidol isomer mixture is added to thepotassium acid sulfate/Primol® mixture at a rate equal to the rate ofcondensed distillate. Thus, the distillation of the farnesene isomermixture is carried out simultaneously with the addition of the nerolidolto the dehydrating medium. The fractions collected are as follows:

    ______________________________________                                        Fraction Vapor    Liquid     Pressure                                         No.      Temp °C.                                                                        Temp °C.                                                                          MM Hg. Wt (g)                                    ______________________________________                                        1        114/127  193/188    15/15  330.3                                     2        130      189        15     671.4                                     3        125      193        15     875.9                                     4        130      195        15     504.2                                     5        110      195        15     394.2                                                                         2776.0 g.                                 ______________________________________                                    

After the addition is completed, the reaction mass is stirred at190°-200° C. for 1 hour in order to insure complete recovery.

All fractions are bulked, diluted with anhydrous diethyl ether (500 ml),washed with one 1,000 ml portion of 5% sodium carbonate and dried overanhydrous magnesium sulfate. The resulting product is then evaporated ona rotary evaporator whereby the diethyl ether is evaporated.

FIG. 1 is the GLC profile after the base wash. (GLC conditions: 10'×1/8"5% Carbowax column programmed at 100°-220° C. at 4° C. per minute).

The base washed farnesene bulk (2776.0 grams) is strip distilled using a2" Splash column containing glass Raschig rings as column packing,yielding the following fractions:

    ______________________________________                                        Fraction Vapor    Liquid     Pressure                                         No.      Temp °C.                                                                        Temp °C.                                                                          MM Hg. Wt (g)                                    ______________________________________                                        1        83/93    117/122    1/1    496.7                                     2        94       123        1      583.6                                     3        96       128        1      658.2                                     4        109      139        1      596.2                                     5        125      205        1      265.8                                                                         2600.5 g.                                 ______________________________________                                    

All fractions are then bulked (2600.5 grams) and fractionated on a 12"vacuum jacketed glass column containing glass Raschig rings as columnpacking, yielding the following fractions:

    ______________________________________                                        Fraction                                                                             Vapor    Liquid    Pressure                                                                             Reflux                                       No.    Temp °C.                                                                        Temp °C.                                                                         MM Hg. Ratio  Wt (g)                                ______________________________________                                        1      46/54    135/132   1.4/1.0                                                                              9:1    69.5                                  2      51       130       0.9    9:1    87.4                                  3      52       132       0.8    9:1    99.4                                  4      70       133       1.4    9:1    45.1                                  5      63       134       0.9    9:1    109.0                                 6      53/52    127/129   0.8/0.7                                                                              9:1    98.4                                  7      52       131       0.7    9:1    136.3                                 8      51       130       0.7    9:1    117.1                                 9      52       133       0.7    9:1    151.2                                 10     52       135       0.7    9:1    166.3                                 11     62/61    133/133   0.7/0.7                                                                              9:1    88.8                                  12     81       145       2.0    9:1    68.7                                  13     71       130       2.0    9:1    91.2                                  14     73       132       2.0    9:1    94.1                                  15     65/73    130/131   1.2/1.1                                                                              9:1    58.8                                  16     61       129       1.2    9:1    79.1                                  17     73       131       1.2    9:1    141.6                                 18     62       137       0.6    9:1    116.5                                 19     50/59    133/138   0.7/0.6                                                                              9:1/4:1                                                                              99.8                                  20     63       138       0.6    3:2    119.5                                 21     45       204       1.4    3:2    87.2                                                                          2125.0 g                              ______________________________________                                    

Fractions 4-18 (1562.2 grams) are bulked.

FIG. 2 is the GLC profile for bulked fractions 4-18.

In FIG. 2, peak 11 indicates the compound having the structure:##STR35##

Peak 12 indicates the compound having the structure: ##STR36##

Peak 13 indicates the compound having the structure: ##STR37##

Peak 14 indicates the compounds having the structures: ##STR38## whereinthe structure: ##STR39## one of the dashed lines represents a pi doublebond and each of the other dashed lines represent single bonds.

Peaks 15A and 15B are indicative of the compounds having the structures:##STR40## the isomers of nerolidol.

FIGS. 3, 4, 5 and 6 are infra-red spectra of, respectively, peaks 11,12, 13 and 14 of FIG. 2.

FIGS. 7, 8, 9 and 10 are, respectively, NMR spectra for peaks 11, 12, 13and 14 of FIG. 2.

FIGS. 11, 12, 13 and 14 are, respectively, mass spectra for peaks 11,12, 13 and 14 of FIG. 2.

Bulked fractions 14-18 have a very natural waxy, flowery,(magnolia-like, tuberose-like, gardenia-like) aroma with citrusy(lemon/lime), petitgrain-like undertones and green top notes.

EXAMPLE II ISOLATION OF α-FARNESENE ISOMER MIXTURE FROM NAGNOLIAHEADSPACE

The volatiles of two magnolia blossoms (Cadiz, Spain) were entrained onCarbowax 20 by sweeping the petals with helium for 24 hours. The trap isthen analyzed by GLC analysis on a 500'×0.03" SF-96 capillary column.

FIG. 16 is the GLC profile for this headspace. Reference numeral 16 isindicative of the α-farnesene isomers contained in the headspace. Suchα-farnesene isomers are represented by the structures: ##STR41##

EXAMPLE III PREPARATION OF ISOMERIC FARNESENE MIXTURE FROM NEROLIDOLMIXTURE USING PARATOLUENE SULFONIC ACID CATALYST ##STR42## (wherein inthe structure: ##STR43## one of the dashed lines is indicative of a pidouble bond and each of the other of the dashed lines is indicative ofsingle bonds, said structure: ##STR44## being indicative of a mixture ofthree compounds).

Into a two liter, three-neck reaction flask equipped with mechanicalstirrer, reflux condenser, Bidwell water separater, thermometer andheating mantle is added 500 grams of a nerolidol isomer mixturecontaining compounds having the structures: ##STR45## defined morespecifically according to the GLC profile of Figure B, and one gram ofparatoluene sulfonic acid.

The reaction mass is stirred at room temperature for a period of 2hours. The reaction mass is then refluxed for a period of 3 hours until40 ml of water is removed. The reaction mass is then washed with oneportion of 200 ml of 5% sodium carbonate and two 100 ml portions ofwater. The resulting organic layer is dried over anhydrous magnesiumsulfate, filtered and the solvent is removed at atmospheric pressure.

The crude reaction mass is then analyzed on a GLC column.

FIG. 16(A) is the GLC profile for the crude product. (Conditions:10'×1/8" 5% Carbowax column programmed at 100°-240° C. at 4° C. perminute.)

The crude reaction mass is then distilled using a 4" column containingglass rings as packing and a Rushover head.

The distillation fractions are as follows:

    ______________________________________                                                  Vapor   Liquid           Weight of                                  Fraction  Temp.   Temp.     Pressure                                                                             Fraction                                   Number    (°C.)                                                                          (°C.)                                                                            mm/Hg. (grams)                                    ______________________________________                                        1         82/85   103/104   1.8/1.8                                                                              22.8                                       2         87      104       1.8    33.6                                       3         89      105       1.8    51.3                                       4         89      108       1.8    51.1                                       5         90      111       1.8    50.6                                       6         90      115       1.8    46.6                                       7         92      118       1.8    51.1                                       8         94      155       1.8    22.4                                       9         100     200       1.8    11.5                                       ______________________________________                                    

Fractions 4-7 are bulked. These fractions have a pleasant waxy, flowery(magnolia-like, tuberose-like, gradenia-like), wet petal aroma withcitrusy (lemon/lime) petitgrain-like undertones and green top notes.

FIG. 16(B) is the GLC profile for fraction 1 of the foregoingdistillation (conditions: 10'×1/8" 5% Carbowax column programmed at100°-220° C. at 4° C. per minute). The conditions for the following GLCanalysis are the same.

FIG. 16(C) is the GLC profile for fraction 2.

FIG. 16(D) is the GLC profile for fraction 3.

FIG. 16(E) is the GLC profile for fraction 4.

FIG. 16(F) is the GLC profile for fraction 5.

FIG. 16(G) is the GLC profile for fraction 6.

FIG. 16(H) is the GLC profile for fraction 7.

FIG. 16(J) is the GLC profile for fraction 8.

FIG. 16(K) is the GLC profile for fraction 9.

FIG. 16(L) is the GLC profile for bulked fractions 4-7.

FIG. 17 is the infra-red spectrum for bulked fractions 4-7 of theforegoing distillation.

EXAMPLE IV ATTEMPTED PREPARATION OF ODOR ACCEPTABLE MIXTURE OF FARNESENEISOMERS USING ACETIC ANHYDRIDE DEHYDRATION REAGENT

Into a one-liter distillation flask equipped with thermometer,condenser, separatory funnel (containing dry ice), magnetic stirrer andheating mantle under a nitrogen atmosphere is placed 200 grams ofnerolidol, a 65:35 mixture of the isomers having the structures:##STR46## obtained from the Givaudan Corporation of Clifton, New Jerseyand 500 ml acetic anhydride. The reaction mass is refluxed at 130°-140°C. for a period of 4 hours.

The reaction mass is then added to 300 grams of ice in a separatoryfunnel.

The organic layer and the aqueous layer are separated. The organic layeris washed with a 10% solution of sodium carbonate followed by saturatedsodium chloride solution. The organic layer is dried over anhydrousmagnesium sulfate and the solvent is evaporated on a rotary evaporator.

The weight of the crude material is 237.8 grams.

The resulting crude material is distilled on a Spinning Band columnyielding the following fractions:

    ______________________________________                                                Vapor     Liquid            Weight of                                 Fraction                                                                              Temp.     Temp.     Pressure                                                                              Fraction                                  Number  (°C.)                                                                            (°C.)                                                                            mm/Hg.  (grams)                                   ______________________________________                                        1        88/101   148/150   20/20   2.0                                       2       102       151       20      3.2                                       3       103       151       20      3.0                                       4       102       151       19      2.4                                       5       106       159       20      3.8                                       6       111       151       20      3.5                                       7       115       155       20      3.4                                       8        70       160       ?       2.5                                       9       103/112   161/161   20/20   3.6                                       10      111       161       20      3.6                                       11      110       161       20      3.6                                       12      106       166       20      3.2                                       13       93       166       20      3.1                                       14       93       166       20      3.1                                       15      102       168       20      2.3                                       16      102       168       20      2.7                                       17      100       170       20      2.4                                       ______________________________________                                    

Fractions 6-12 are then re-distilled on a Micro-Vigreux column to yieldthe following fractions:

    ______________________________________                                                Vapor     Liquid            Weight of                                 Fraction                                                                              Temp.     Temp.     Pressure                                                                              Fraction                                  Number  (°C.)                                                                            (°C.)                                                                            mm/Hg.  (grams)                                   ______________________________________                                        1        83/111    95/115   1.1/0.9 3.0                                       2       105       113       0.5     3.3                                       3       95        110       0.5     2.2                                       4       85         98       0.5     2.7                                       5       76         93       0.5     1.9                                       6       78         98       0.5     2.3                                       7       79         98       0.5     2.4                                       8       75        110       0.5     2.1                                       9       50        190       0.5     0.6                                       ______________________________________                                    

Fractions 4-8 are bulked and odor evaluated.

FIG. 18 is the GLC profile for the crude reaction product (conditions:10'×1/8" 5% Carbowax column programmed at 220° C. isothermal).

FIG. 19 is the GLC profile for bulked fractions 4-8 of the foregoingdistillation (conditions: 10'×1/8" 5% Carbowax column programmed at 200°C. isothermal).

In FIG. 18, peaks 17A and 17B are indicative of farnesene isomerswhereas peaks 18A, 18B and 18C are indicative of farnesyl acetateisomers as indicated by the structures: ##STR47##

More particularly, in FIG. 19, peak 19A signifies the compound havingthe structure: ##STR48##

Peak 19B signifies the compound having the structure: ##STR49##

Peak 19C signifies the compound having the structure: ##STR50##

Peak 19D signifies the compound having the structure: ##STR51##

Insofar as the proportions of isomers in fractions 1-9 are concerned,these are as follows:

    ______________________________________                                        Fraction Weight     Peak   Peak   Peak Peak                                   Number   (grams)    19A    19B    19C  19D                                    ______________________________________                                        1        3.0        10.8   22.8   16.1 31.4                                   2        3.3        9.6    21.6   16.5 33.5                                   3        2.2        8.3    20.4   16.6 36.0                                   4        2.7        8.0    20.0   16.6 37.0                                   5        1.9        7.6    19.6   16.7 37.5                                   6        2.3        6.1    17.5   16.4 38.4                                   7        2.4        4.4    15.1   17.0 44.7                                   8        2.1        2.9    11.7   16.0 49.0                                   9        0.6        1.3    7.6    13.4 49.0                                   ______________________________________                                    

The resulting bulked fractions 4-8 have a fresh, smooth, rosy, citrusnote. The citrus part has a lemon/lime/petitgrain aroma which is veryintense. Also present are strong terpenic notes. The material has noneof the "wet petal", "white flower" aroma nuances produced according toExamples I and III. In addition, the material produced according to theinstant example has fatty, orangy, licorice-like, and metallicundertones which cause it to lack usefulness in substantially allperfumery areas and all perfumed article areas.

EXAMPLE V ELUCIDATION OF RANGE OF OPERABLE VARIABLES OF INVENTION

EXAMPLE V(A)

PRODUCTION OF FARNESENE ISOMER MIXTURE USING POTASSIUM ACID SULFATECATALIST AT 150° C. ##STR52##

Into a three liter reaction vessel equipped with 6" Splash columnRushover head, mechanical stirrer, addition funnel, thermometer, andfraction cutter, is placed 500 grams Primol and 50 grams potassium acidsulfate (KHSO₄). The mixture is heated to 190° C. while keeping thesystem under 5 mm/Hg vacuum.

The resulting mixture is maintained at 190° C. for 30 minutes in orderto "melt" the potassium acid sulfate crystals.

The resulting mixture is then cooled to 150° C. and over a period of 6hours nerolidol having a GLC profile as set forth in Figure A is addedto the reaction mass dropwise from the addition funnel. The isomers ofnerolidol in the nerolidol reactant are: ##STR53## The addition rate ofthe nerolidol is adjusted to equal the "take off rate" of the product.After the addition is completed, the heating is continued until noadditional liquid is distilled.

The reaction mass is then rinsed with toluene into a separatory funnel.The resulting organic layer is washed with 1 volume of 5% sodiumcarbonate and 2 volumes of water. The organic layer is then dried overanhydrous magnesium sulfate and stripped distilled and rushed overyielding the following fractions:

    ______________________________________                                                  Vapor   Liquid           Weight of                                  Fraction  Temp.   Temp.     Pressure                                                                             Fraction                                   Number    (°C.)                                                                          (°C.)                                                                            mm/Hg. (grams)                                    ______________________________________                                        1         74/90   92/97     3      75.4                                       2          91      98       2      79.3                                       3          92     100       2      92.9                                       4          93     100       2      81.7                                       5          93     100       2      86.5                                       6          96     104       2      88.0                                       7          99     106       2      88.0                                       8         101     108       2      95.2                                       9         103     109       2      86.9                                       10        103     109       2      89.1                                       11        103     109       2      83.9                                       12        103     112       2      85.7                                       13        103     114       2      81.5                                       14        112     145       2      86.3                                       15        155     210       2      51.3                                       ______________________________________                                    

Fractions 7-11 are bulked and have a waxy, flowery, wet petal aromareminiscent of magnolia, tuberose, and gardenia with jasmin top notes.

EXAMPLE V(B)

ATTEMPTED PRODUCTION OF FARNESENE ISOMERS USING CYCLOHEXANE SOLVENT ANDPOTASSIUM ACID SULFATE CATALYST

Into a 3 liter reaction flask equipped with thermometer, condenser,bidwell trap, mechanical stirrer and heating mantle is placed 1000 grams(4.5 moles) of nerolidol having a GLC profile in accordance with FigureA, 20.0 grams of potassium acid sulfate and 600 ml cyclohexane. Theresulting mixture is heated to reflux and 4.5 moles (80 grams) of waterare collected. The refluxing proceeds for a period of 4 hours. At theend of the refluxing, the reaction mass is washed with 1 volume of 5%sodium carbonate and 1 volume of water. The reaction mass is then driedover anhydrous magnesium sulfate and stripped atmospherically to yield920 grams of crude product. The resulting crude product is thendistilled on a 2 liter-short Splash column packed with saddles to yieldthe following fractions:

    ______________________________________                                                 Vapor   Liquid            Weight of                                  Fraction Temp.   Temp.      Pressure                                                                             Fraction                                   Number   (°C.)                                                                          (°C.)                                                                             mm/Hg. (grams)                                    ______________________________________                                        1        78/87   101/108    0.95/0.90                                                                            78.7                                       2         88     111         0.90  83.8                                       3         89     111        0.9    82.5                                       4         89     115        0.9    100.8                                      5         89     126        0.9    95.1                                       6        112     158        0.9    85.5                                       7        120     181        1.1    83.2                                       8        120     205        1.1    94.6                                       9        123     214        1.1    68.6                                       10       112     225        1.0    32.5                                       ______________________________________                                    

The resulting product has a terpenic character and is unsuitable for usein perfumery. It does not have the "wet petal", waxy, flowery aromafound in the reaction product of Example V(A), I or III.

EXAMPLE V(C)

ATTEMPTED PRODUCTION OF FARNESENE ISOMERS USING TOLUENE SOLVENT ANDPOTASSIUM BISULFATE DEHYDRATING CATALYST

Into a 5 liter reaction flask equipped with mechanical stirrer, heatingmantle, thermometer, bidwell trap and reflux condenser is placed 1000.0grams (4.5 moles) of nerolidol having a GLC profile according to FigureA, 600 ml tolune and 16.7 grams of potassium bisulfate (KHSO₄). Theresulting mixture is heated to reflux (110° C.) and heating is continueduntil the theoretical amount of water, 81 grams (4.5 moles) arecollected.

The water take-off proceeds for a period of 5.5 hours.

The reaction mass is then transferred to a 5 liter separatory funnel and1000 ml of 5% sodium carbonate solution are added in order to wash theproduct. The organic and aqueous layers are then separated and theorganic layer is dried over anhydrous magnesium sulfate. The resultingproduct is then filtered by gravity into a 3 liter distillation flaskand rushed over on a short splash column packed with glass Raschig ringsyielding the following fractions:

    ______________________________________                                                  Vapor   Liquid           Weight of                                  Fraction  Temp.   Temp.     Pressure                                                                             Fraction                                   Number    (°C.)                                                                          (°C.)                                                                            mm/Hg. (grams)                                    ______________________________________                                        1         25/30   40/68     20/5   107.1                                      2          98     112       2      99.5                                       3         100     115       2      103.4                                      4         100     117       2      103.0                                      5         100     120       2      85.6                                       6         100     128       2      99.9                                       7         100     138       2      98.5                                       8         108     179       2      63.8                                       9         110     205       2      85.9                                       10        150     225       2      37.9                                       ______________________________________                                    

The resulting product is then redistilled on an 18" glass column packedwith Raschig rings to yield the following fractions:

    ______________________________________                                                 Vapor   Liquid            Weight of                                  Fraction Temp.   Temp.      Pressure                                                                             Fraction                                   Number   (°C.)                                                                          (°C.)                                                                             mm/Hg. (grams)                                    ______________________________________                                        1        64/68   113/120    1.2/1.1                                                                              42.7                                       2        70      121        1.1    60.4                                       3        70      122        1.0    77.3                                       4        73      127        1.1    64.6                                       5        74      128        1.1    80.9                                       6        76      130        1.2    93.6                                       7        85      135        1.6    88.4                                       8        78/84   138/140    1.1/1.1                                                                              38.9                                       9        92      177        1.0    93.3                                       10       93      215        1.6    54.3                                       ______________________________________                                    

The resulting product and each of the individual fractions are eachincapable of being useful in perfumery in view of their terpinic,nerolidol-like character.

EXAMPLE VI MAGNOLIA FORMULATION

To demonstrate the use of the farnesene isomer mixture producedaccording to Examples I, II and V(A) in a magnolia formulation, thefollowing formula is provided:

    ______________________________________                                        Ingredients           Parts by Weight                                         ______________________________________                                        Phenylethyl alcohol   200                                                     Geraniol              400                                                     Trichloromethylphenyl carbinyl                                                acetate               20                                                      Phenylethyl acetate   60                                                      Undecylenic aldehyde (10% in                                                  diethyl phthalate)    5                                                       n-nonyl aldehyde (10% in diethyl                                              phthalate)            2                                                       Musk ketone           10                                                      Musk ambrette         10                                                      Eugenol phenyl acetate                                                                              20                                                      Citronellol           100                                                     Vanillin (10% in diethyl phthalate)                                                                 6                                                       Eugenol               30                                                      Citronellyl formate   30                                                      Geranyl acetate       10                                                      Linalool              40                                                      Geranyl phenyl acetate                                                                              50                                                      Cis beta, γ-hexenyl acetate                                                                   2                                                       1-(2,5,5-trimethyl-1,3-cyclohexadien-                                         1-yl)-1,3-butanedione 5                                                       Farnesene isomer mixture produced                                             according to either of Example I, III                                         or V(A)               180                                                     ______________________________________                                    

The addition of the farnesene isomer mixture of either of Examples I,III or V(A) lends a great deal of strength and character to the magnoliafragrance imparting to it a waxy, flowery aroma with an intense wetpetal character reminiscent of white flowers. At lower concentrations,the farnesene isomer mixtures are more subtle, however, they still yieldan interesting natural effect with the white flower, waxy, wet petalundertone.

EXAMPLE VII PREPARATION OF A SOAP COMPOSITION

One hundred grams of soap chips are produced according to Example V ofU.S. Pat. No. 4,058,487 issued on Nov. 15, 1977 as follows:

The sodium salt of an equal mixture of C₁₀ -C₁₄ alkane sulfonates (95%active), 40 pounds, is dissolved in a mixture of 80 pounds of anhydrousisopropanol and 125 pounds of dionized water at 150° F. In this mixtureis dissolved 10 pounds of partially hydrogenated coconut oil, fattyacids and 15 pounds of sodium mono-C₁₄ -alkylmaleate and the pH of thesolution is adjusted to 6.0 by the addition of a small amount of a 50%aqueous solution of sodium hydroxide. The isopropanol is distilled offand the remaining aqueous solution is drum dried. The resulting solidactives are then blended in a chip mixture with 10 pounds of water, 0.2pounds titanium hydroxide and 0.75 pounds of one of the materials setforth in Table I below:

                  TABLE I                                                         ______________________________________                                        Perfume Ingredient                                                                              Aroma Profile                                               ______________________________________                                        Perfume material of                                                                             An intense, magnolia                                        Example VI        aroma with pleasant                                                           wet petal, waxy and                                                           flowery nuances and an                                                        extremely natural                                                             character.                                                  One of the farnesene                                                                            A waxy, flowery, natural                                    isomer mixtures produced                                                                        white flower (tuberose,                                     according to Example I,                                                                         magnolia, jasmine and                                       III or V(A)       gardenia) aroma with                                                          interesting wet petal                                                         characteristics.                                            ______________________________________                                    

The chips are then plodded into logs, cut to size and finally stampedinto bars, having a pH of approximately 6.9.

Each of the perfumed soaps of Table I above manifests an excellentcharacteristic as indicated in Table I above.

EXAMPLE VIII PREPARATION OF A DETERGENT COMPOSITION

A total of 100 grams of a detergent powder prepared according to U.S.Pat. No. 4,058,472 and containing 5% by weight of the sodium salts of amixture of sulfonated C₁₄ -C₁₈ alkyl catechol as a surface activecomponent, the mixture being 60 parts by weight of mono-C₁₄ -C₁₈ alkylcatechol and 40 parts by weight of di-C₁₄ -C₁₈ alkyl catechol, 35% ofsodium tetrapyrophosphate, 30% of sodium silicate, 20% of sodiumcarbonate, 3% of sodium carboxymethyl cellulose and 7% of starch ismixed with 0.15 grams of one of the perfume ingredients of Table I ofExample VII, supra, until a substantially homogeneous composition isobtained. This composition has an excellent aroma as indicated accordingto Table I of Example VII, supra.

EXAMPLE IX PREPARATION OF COSMETIC POWDER COMPOSITIONS

A cosmetic powder is prepared by mixing in a ball mill 100 grams oftalcum powder with 0.25 grams of one of the perfume materials of Table Iof Example VII, supra. Each of the cosmetic powders has an excellentaroma as set forth in Table I of Example VII, supra.

EXAMPLE X PERFUMED LIQUID DETERGENTS

Concentrated liquid detergents having aromas as set forth in Table I ofExample VII, supra, are prepared by adding 0.10%, 0.15% and 0.20% ofeach of the perfume ingredients of Table I of Example VII, supra. Theyare prepared by adding and homogeneously mixing the appropriate quantityof perfume material in the liquid detergent. The detergents all possessaromas as set forth in Table I of Example VII, supra.

EXAMPLE XI PREPARATION OF COLOGNE AND HANDKERCHIEF PERFUMES

Each of the compositions of Table I of Example VII, supra, isincorporated into colognes at several concentrations, 2.0%, 2.5%, 3.0%,3.5%, 4.0%, and 5.0% in 70%, 75%, 80%, 85% and 90% aqueous ethanol; andinto handkerchief perfumes at concentrations of 10%, 15%, 20% and 25%(in 80%, 85%, 90% and 95% aqueous ethanol). The use of each of theperfume ingredients as set forth in Table I of Example VII, supra,affords distinctive aromas as set in Table I of Example VII, supra.

EXAMPLE XII PREPARATION OF A DETERGENT COMPOSITION

A total of 100 grams of a detergent powder (a nonionic detergent powdercontaining a proteolytic enzyme prepared according to Example I ofCanadian Pat. No. 985,190 issued on Mar. 9, 1976) is mixed with 0.15grams of a perfume material set forth in Table I of Example VII, supra,until a substantially homogeneous composition is obtained in each case.Each of the compositions has an excellent aroma as set forth in Table Iof Example VII, supra.

EXAMPLE XIII

Utilizing the procedure of Example I at column 15 of U.S. Pat. No.3,632,396 (which is hereby incorporated by reference into the instantspecification), a nonwoven cloth substrate useful as a dryer-addedfabric softening article of manufacture is prepared wherein thesubstrate, the substrate coating and the outer coating and the perfumematerial are as follows:

1. a water "dissolvable" paper ("Dissolvo Paper");

2. Adogen 448 (m.p. about 140° F.) as the substrate coating; and

3. an outer coating having the following formulation (m.p. about 150°F.):

57% C₂₀₋₂₂ HAPS

22% isopropyl alcohol

20% antistatic agent

1.5% of one of the perfume materials of Table I of Example VII, supra.

A fabric softening composition prepared as set forth above having anaroma characteristic as set forth in Table I of Example VII, supra,consists of a substrate having a weight of about 3 grams per 100 squareinches, a substrate coating of about 1.85 grams per 100 square inches ofsubstrate and an outer coating of about 1.4 grams per 100 square inchesof substrate, thereby providing a total aromatized substrate and anouter coating weight ratio of about 1:1 by weight of the substrate. Theresulting aromas can be described as set forth in Table I of ExampleVII, supra, and are imparted in pleasant manners to the head space inthe dryer on operation thereof using said dryer-added fabric softeningnonwoven fabric.

EXAMPLE XIV PERFUMED POLYETHYLENE

Scented polyethylene pellets having a pronounced aroma as set forth inTable I of Example VII, supra, are prepared as follows (in accordancewith Example III of U.S. Pat. No. 3,505,432 which is incorporated byreference herein):

75 pounds of polyethylene of a melting point of about 220° F. are heatedto about 230° F. in a container as illustrated in FIGS. 1 and 2 of U.S.Pat. No. 3,505,432. 25 pounds of one of the perfume materials of Table Iof Example VII, supra, are then quickly added to the liquifiedpolyethylene, the lid is put in place and the agitating means areactuated. The temperature is maintained at about 225° F. and the mixingis continued for about 15 minutes. The valve is then opened to allowflow of the molten polyethylene enriched with the perfume containingmaterial to exit through the orifices as indicated in FIGS. 1 and 2. Theliquid falling through the orifices solidifies almost instantaneouslyupon impact with the moving cooled conveyor. Solid polyethylene beads orpellets having a pronounced aroma as set forth in Table I of ExampleVII, supra, are thus formed. Analysis demonstrates that the pelletscontain about 25% of the perfume substance of Table I of Example VII,supra, so that almost no losses of the scenting substance occur. Thesepellets may be called master pellets. 50 pounds of the perfume substancecontaining master pellets are then added to 100 pounds of unscentedpolyethylene powder and the mass is heated to the liquid state. Theliquid is molded into thin sheets or films. The sheets or films have apronounced aroma as set forth in Table I of Example VII, supra.

EXAMPLE XV SCENTED POLYPROPYLENE

100 pounds of polypropylene are heated to about 300° F. 30 pounds of oneof the aroma materials of Table I of Example VII, supra, are added tothe liquified polypropylene. The procedure is carried out in theapparatus of FIGS. 1 and 2 of U.S. Pat. No. 3,505,432. After mixing forabout 8 minutes, the valve is opened to allow the exit of thepolypropylene-scented material mixture whereby solid pellets having apronounced aroma as set forth in Table I of Example VII, supra, areformed on the conveyor. The pellets thus obtained are then admixed withabout 20 times their weight of unscented polypropylene and the mixtureis heated and molded into flat discs. The flat discs have a strong andpleasant aroma as set forth in Table I of Example VII, supra.

EXAMPLE XVI

A perfumed polymer is produced by admixing a microporous polymerproduced according to one of Examples 194-236 of U.S. Pat. No. 4,247,498(the disclosure of which is incorporated by reference herein), andapplying a 0.5 mm/Hg vacuum to the system. The resulting product is thencompressed into pellets and molded into fragrance-emitting plasticobjects, e.g. automobile dashboards.

What is claimed is:
 1. A process for augmenting or enhancing the aromaof a solid or liquid anionic, cationic, nonionic or zwitterionicdetergent comprising the step of adding to a solid or liquid anionic,cationic, nonionic or zwitterionic detergent base an aroma augmenting orenhancing quantity of a farnesene isomer mixture produced according tothe process of dehydrating a nerolidol isomer mixture containingnerolidol isomers defined according to the structures: ##STR54## in thepresence of a catalyst selected from the group consisting of potassiumacid sulfate and paratoluene sulfonic acid at a temperature in the rangeof from 110° C. up to 200° C. and at a pressure in the range of from 1mm/Hg pressure up to 200 atmospheres pressure, absolute.
 2. The processof claim 1 wherein in the dehydrating process, the dehydration agent ispotassium acid sulfate, the process is carried out in the presence of ahydrocarbon mineral oil solvent and the process is carried out at atemperature in the range of from 150° up to 200° C. at from 1 mm/Hgpressure up to 25 mm/Hg pressure.
 3. The process of claim 1 wherein inthe dehydrating process the dehydrating agent is paratoluene sulfonicacid and the reaction temperature ranges from 115° C. at atmosphericpressure, at reflux, up to 200° C. at reflux and the reaction takesplace in the presence of a solvent selected from the group consisting oftoluene, xylene and a heavy hydrocarbon mineral oil.